Crosslinked polymers containing siloxane groups

ABSTRACT

New crosslinked polyamides, polyimides and polyamide-imides containing siloxane groups are described, which can be manufactured by heating silicon-modified polyamide, polyamideacid and polyamide-amide-acid prepolymers to temperatures of between 50* and 350*C. These crosslinked polymers containing siloxane groups are distinguished by good mechanical, electrical and thermal properties.

ilnited States Patent Greber et a1.

[ Dec. 16, 1975 CROSSLINKED POLYMERS CONTAINING SILOXANE GROUPSInventors: Gerd Greber, Binningen; Roland Darms, Therwil; DieterLohmann, Pratteln, all of Switzerland Assignee: Ciba-Geigy Corporation,Ardsley,

Filed: May 24, 1974 Appl. No.: 473,047

Foreign Application Priority Data June 7, 1973 Switzerland 8259/73 Aug.2, 1973 Switzerland 11230/73 U.S. CL... 260/46.5 E; 260/46.5 G; 260/47CP; 260/78 TF; 260/824 R Int. Cl. C08G 77/04; C08G 77/26 Field of Search260/46.5 E, 78 TF, 47 CP, 260/824 R, 46.5 G

[56] References Cited UNITED STATES PATENTS 3,288,754 11/1966 Green260/465 E 3,779,990 12/1973 Greber et a1 260/47 CP PrimaryExaminerMelvyn l. Marquis Attorney, Agent, or FirmLuther A. R. Hall [57]ABSTRACT siloxane groups are distinguished by good mechanical,

electrical and thermal properties.

12 Claims, No Drawings cyclised derivatives, are heated totemperaturesbe- CROSSLINKED POLYMERS CONTAINING tween 50 and 350C. 1

SILOXANE GROUPS Heating to temperatures between 150 and 225C ispreferred.

The present invention relates to new crosslinked 5 Silicone-modifiedpolyamide, polyamide-acid and polyamides, polyimides andpolyamide-imides containpolyamide-amide-acid prepolymers which can beused ing siloxane groups, a process for their manufacture according tothe invention preferably have an inherent and their use as industrialproducts. viscosity of 0.07 to 2.5.

It has been found that new crosslinked polyamides, The inherentviscosity 1;,-,,,, is calculated from the polyimides andpolyamide-imides, containing from 0.1 following equation: to 17.0percent by weight of silicon and exhibiting improved properties can beobtained when siliconmodified polyamide, polyamide-acid or polyamide- In1 amide-acid prepolymers with an inherent viscosity of m h 0.04 to 4.0,which have the formula I I C 0v y In this equation, the symbols havingthe following meaning: 1n natural logarithm, "q viscosity of the Q -:ll-(I) 1 solution (0.5 percent by weight of the polymer in a Y Y suitablesolvent, for example, N,N-dimethylacetamide,

N,N-dimethylformamide or N-methylpyrrolidone), 7

wherein X represents a Structural element of the viscosity of thesolvent and c concentration of the mula H polymer solution in g ofpolymer/ 100 ml of solvent.

0 ,0 C// coon HOOC )m-l lmkkf (HOOC),,,( fi NH R., N1-i fi gcoom O a O-The viscosity measurements are carried out at C.

7 As is generally known, the inherent viscosity represents a denotes anumber from 0 to 100, especially 0 to 60 a measure of the molecularweight of a polymer. The and the individual m R1 R2, R3, Q and Y indepenquotedvalues of n ,,,,.=0.04 to 4.0 correspond to averdently of oneanother denote the following: in denotes age molecular Welghts of about400 to The the number 1 or 2 R1 denotes a radical average molecularweights can be determined by methf ods which are in themselves known,for example by means'of light scattering. T 4O Prepolymers according tothe definition, with structural elements X of the formula II, wherein aa 1 and the individual m, R and/or R can have different mean- H o rings, can be homopolymers or copolymers with a statis- X ticaldistribution or with any desired at least partially block-likearrangement of polyamide, polyamide-acid and/or polyamide-amide-acidunits according to the invention in the structural element X, and canbe, for

example, homopolymers or block copolymers with with x denoting a numberfrom 1 to 4, R denotes a termmal aeld groupscarbocyclic-aromatic orheterocyclic radical, wherein Thus; prepolymers of the formula I interalia also the Carbonamide and carboxyl groups are bonded to compriseprepolymers wherein the structural element different ring carbon atomsand the carboxyl groups X be represented by the formula Ha wherein a,denotes a number from 0 to 99 and k and p are each in the ortho-positionto a carbonamide group, independently of one another denote the number 1or R denotes an aliphatic radical with at least 2 carbon 2 and what hasbeen stated under the formula 1 applies atoms, or a cycloaliphatic,araliphatic, carbocyclicto R R R m, Q and Y, and the correspondingcyaromatic or heterocyclic radical, Q denotes methyl, clisedderivatives. phenyl or an-OY radical, with Y having the meaningSilicon-modified prepolymers of the formula I which indicated below, andY denotes an alkyl radical with 1 can be used according to theinvention, and wherein X to 6 carbon atoms or a phenyl radical, orcorresponding represents a structural element. of the formula II or lIa,

3 4 and corresponding cyclised derivatives, can be manu-Silicon-modified prepolymers which can be used factured by reacting, ifa O, dicarboxylic acid dichloaccording to the invention, of the formulaI, wherein X rides of the formula represents a structural element of theformula [Ia and k 2, can also be obtained according to a modified pro- 5cess by reacting at least 2 mols of a compound of the ll formula IVtricarboxylic acid anhydride chlorides of the formula ii 0 SI R NH C c lo H H OY 7 R 0 C 1 c R C o (Hooc p 1 c wherein p is the number of l or2, the radical -COOH l is in the ortho-position to the grouping -CO-NH-Ror tetracarboxylic acid dianhydrides of the formula nd the anhydridegrouping is bonded to adjoining C atoms of the radical R with a diamineof the formula H N-R -NH if a 0, or a polyamide, a polyamide- 0 acid ora polyamide-amide-acid, if a =l, of the O O l formula V C l I c(HOOC),,, C NHR3-NHQ v or, if a a l, polyamides or polyamide-amide-acidswith 2 id hl id d groups, polyamide acids or 1 or corresponding cyclisedderivatives, cyclised derivamide-al'nide-acids with 2 anhydride endgroups or tives, the statements under formula I or Ilaapplypolyamide-amide-acids with one acid chloride and one g t0 1 m, P 1,2, 3, Q 1 a p l y anhydride end group, all these apart from said endSubsequently chemlcany cycllsmg ShCOn-modlfied groups corresponding tothe formula II, or correpolyamide'acid or P -e e P PP Y spondingcyclised derivatives, with at least 2 mols of an If 2 represents aearbeeyehe-arematle radleel, h aminosilane of the formula III 40 latterpreferably has at least one 6-membered ring; in

particular, these are monocylic radicals, fused polycyclic radicals orpolycyclic radicals with several cyclic,

Y n s fused or non-fused systems, which can be linked to one anotherdirect or via bridge members.

Y As examples of suitable bridge members there may be mentioned:

O i) O O Q,

wherein what has been stated under the formula lapplies to a, m, R R R Qand Y, and optionally subsewherein Qi represents an alkyl or alkyleneradical with quently chemically cyclising silicon-modified polyal to 6,preferably 1 to 4, carbon atoms, which can mide-acid orpolyamide-amideacid prepolymers. optionally by substituted by halogenatoms, preferably v 3,926,91 l 6 fluorine, or a cycloalkyl, aryl orarylene radical and Q Particularly preferentially, R represents the 1,4-or represents hydrogen, an alkyl radical with l to 4 carbon1,3-phenylene radical or a benzene ring or the benzoatoms, which canoptionally be substituted by halogen phenone ring system and Rrepresents the l,4- or 1,3- atoms, a cycloalkyl radical or an arylradical. Such phenylene radical, the 4,4-diphenylyl-ether radical orradicals can also be bonded to one another via two 5 the 4,4-diphenylylmethane radical, but of R and R bridge members, such as two -SOgroups. onlyone denotes a 1,4-phenylene radical.

If R denotes a heterocyclic radical, it can in particu- The followingmay be mentioned as examples of alkyl lar be a S-membered or 6-memberedheterocyclicradicals with l to 6 carbon atoms which Y represents:aromatic, optionally benzo-condensed ring systems methyl, ethyl,n-propyl, iso-propyl, n-butyl, tert.-butyl, containing 0, N and/or S. 10n-pentyl and n-hexyl radicals. Preferably, the individualCarboxyIic-aromatic or heterocyclic radicals repre- Y represent an ethylor propyl radical, especially the sented by R can also be substituted,for example by n-propyl radical, whilst Q, if Y ethyl, preferablydenitro groups, alkyl groups with l to 4 carbon atoms, notes the ethoxygroup and, if Y propyl, denotes the trifluoromethyl groups, halogenatoms, especially fluomethyl group. rine, silyl groups or sulphamoylgroups. In general, if a or a 1, prepolymers of the formula Radicalsrepresented by R can be substituted or I with structural elements of theformula II or Ila, substituted, for example by halogen atoms, such aswherein the individual R and R have the same meanfluorine,,chlorine orbromine, or by alkyl or alkoxy ing, k,m and p are the same for eachradical R and groups each with l to 4 carbon atoms. what has been statedunder the formula I applies to R,, If R represents acarbocyclic-aromatic radical, poly- Q and Y, and the correspondingcyclised derivatives, cyclic is preferably a monocyclic, fused polycyclior are preferred. non-fused bicyclic aromatic radical, and in the latterAccording to a further preference, prepolymers of case the aromaticnuclei are bonded to one another via the formula I are used wherein Xrepresents a struca bridge member. Possible bridge members are the turalelement of the formula [lb it it i/ COOH groups mentioned previouslywhen discussing R If R in which a, denotes a number from 1 to 99 and thetwo denotes a heterocyclic radical, it is in particular 21 R eachrepresentabenzene ring, with the carbonamheterocyclic-aromaticS-membered or 6-membered ide and carboxyl groups being bonded todifferent ring ring containing 0, N and/or S. carbon atoms and thecarboxyl groups each being in Possible aliphatic radicals R are aboveall alkylene the ortho-position to the -CO-NH-R grouping, and radicalswith 2 to 12 carbon atoms, and the alkylene the individual R R R Q and Yare identical, or chain can also be interrupted by hetero-atoms, such ascorresponding derivatives with cyclised terminal car- O, S or N atoms.boxylic acid groups, and prepolymers of the formula I If R denotes acycloaliphatic radical it represents, wherein X represents a structuralelement of the forfor example, the cyclohexyl or dicyclohexylmethanemula IIc 2 R (He) radical, whilst possible araliphatic radicals areabove in which a denotes a number from 1 to 99 and the two all, 1,3-,1,4- or 2,4-bis-alkylenebenzene, 4,4'bis-alky- R each denote a benzenering, with the carbonamide lene-diphenyl and4,4-bis-alkylene-d1phenyi-ether radgroups and carboxyl groups beingbonded to different icals. ring carbon atoms and the carboxyl groupsbeing each Preferably, the individual R independently of one i the thosition to th -CO-HN-R grouping, and another represent an unsubstitutedmonocyclic, fused th individual R R R Q and Y are identical, orpolycyclic O no use y li aromatic radical, the corresponding derivativeswith cyclised terminal cararomatic nuclei in the latter case beingbonded to one boxyli id groups.

another via the bridge member -O or -CO-, whilst the The use of thefollowing silicon-modified prepolyindividual R preferably independentlyof one another g i arti larl pref rr d;

denote amon ycli r non-fused bicyclic aromatic Prepolymers of theformula I, wherein X represents a radical which is. optionallysubstituted by halogen structural element of the formula II with m ineach case atOmS 0r alkyl lkoxy groups with 1 to 4 carbon l, or denotes astructural element of the formula Ilb, atoms each, an unsubstitutedmonocyclic araliphatic R i e ch e den t s a radical or an unsubstitutedaliphatic radical possessing 2 to 10 carbon atoms.

7 40-1 4 LCH2.) 3

radical, the individual R and R are respectively indentical and one of Rand R represents the 1,4-phenylene radical and the other the1,3-phenylene radical or R and R each represents the 1,3-phenyleneradical, Q represents the methyl group and Y represents a propyl group,or Q represents the ethoxy group and Y the ethyl group, and what hasbeen stated under the formula II or IIb applies to a, a and R orcorresponding derivatives with cyclised terminal carboxylic acid groups;

prepolymers of the formula I, wherein X denotes a structural element ofthe formula II with m 2 in each case, R in each case represents aradical, R in each case denotes a benzene ring or the benzophenone ringsystem, R in each case denotes the 4,4'-diphenylyl-ether or the4,4'-diphenylylmethane radical, Q denotes the methyl group and Y denotesa propyl group or Q denotes the ethoxy group and Y the ethyl group and ahas the indicated meaning, or corresponding cyclised derivatives;

prepolymers of the formula I, wherein X represents a structural elementof the formula IId if I? coon HOOC c K/ R 2 2 \CNHR=,NH c

ii a ll (Ild) in which R in each case represents a 404 4 (-CH 4 orradical, R in each case represents a benene ring and R in each caserepresents the 4,4-diphenylylether or the 4,4-diphenylylmethane radocal,Q denotes the methyl group and Y denotes a propyl group or Q denotes theethoxy group and Y denotes the ethyl group and a has the indicatedmeaning, or corresponding cyclised derivatives; and

prepolymers of the formula I, wherein X represents a structural elementof the formula llc, R in each case represents a radical, the individualR and R are respectively identical and one of R and R denotes thel,4-phenylene radical and the other the 1,3-phenylene radical or R and Reach denote the 1,3-phenylene radical, Q denotes the methyl group and Ydenotes a propyl group or Q denotes the ethoxy group and Y the ethylgroup and a and R have the indicated meaning, or correspondingderivatives with cyclised terminal carboxylic acid groups.

The starting products which can be used for the manufacture of theprepolymers are in themselves known or can be manufactured according toprocesses which are in themselves known.

Examples of dicarboxylic acid dichlorides of the formula which can beused are thiophene-Z,S-dicarboxylic acid dichloride and terephthalicacid dichloride, but above all isophthalic acid dichloride.

As a tricarboxylic acid anhydride-chloride of the formula it is inparticular possible to use trimellitic acid 1,2- anhydn'de -chloride 1,3-dioxo-benzo c oxalane-S -carboxylic acid chloride).

Examples of tetracarboxylic acid dianhydrides of the formula which canbe used are pyromellitic acid dianhydride,3,3,4,4-benzophenone-tetracarboxylic acid dianhydride,2,3,3,4-benzophenone-tetracarboxylic acid dianhydride, 2,2,3,3-benzophenone-tetracarboxylic acid dianhydride,3,3',4,4'-diphenyltetracarboxylic acid dianhydride,2,2,3,3'-diphenyl-tetracarboxylic acid dianhydride,bis-(2,3-dicarboxyphenyl)-methane diahydride,bis-(3,4-dicarboxyphenyl)-methane dianhydride,2,2-bis-(2,3-dicarboxyphenyl)-propane dianhydride,bis-(3,4-dicarboxyphenyl)-ether dianhydride, bis-(3,4-dicarboxyphenyl)-sulphone dianhydride, N,N- (3,4dicarboxyphenyl)-N-methylamine dianhydride,3,3,4,4'-tetracarboxybenzoyloxybenzene dianhydride,2,3,6,7-naphthalene-tetracarboxylic acid dianhydride,l,2,5,6-naphthalene-tetracarboxylic acid dianhydride,thiophene-Z,3,4,5-tetracarboxylic acid dianhydride,pyrazine-2,3,5,6-tetracarboxylic acid dianhydride andpyridine-2,3,5,6-tetracarboxylic acid dianhydride.

Instead of the abovementioned dianhydrides it is also possible to employcorresponding tetracarboxylic acid diesterdihalides, tetracarboxylicacid diester-diamides, tetracarboxylic acid diamide-dihalides,tetracarboxylic acid diesters or tetracarboxylic acid tetraesters.

Polyamides or polyamide-amide-acids with 2 acid chloride end groups,polyamide-acids or polyamideamide-acids with 2 end groups orpolyamide-amideacids with one acid chloride end group and one anhydrideen group (a B l), which apart from said end groups correspond to theformula II, can be manufactured by reacting an excess of suitablecarboxylic acid derivatives, that is to say dicarboxylic aciddichlorides, tricarboxylic acid anhydridechlorides or tetracarboxylicacid dianhydrides of the abovementioned formulae with one or morediamines of the formula H N-R -NH If at the same time differentcarboxylic acid derivatives are employed, in a total excess over thediamine, copolymers corresponding to the formula II are obtained whichhave identical or different terminal acid groups and a statisticaldistribution of the polyamide, polyamide-acid and/orpolyamide-amide-acid units. If, on the other hand, a single carboxylicacid derivative is used, in excess over the diamine, homopolymers withterminal acid groups are obtained, in which the tenninal acid groupscan, when using a tricarboxylic acid anhydride-chloride, also bedifferent, depending on the type of linking.

Instead of tn'acarboxylic acid anhydride-chlorides it is also possible,in the case of a 2 2, to employ tricarboxylic acid derivatives of theformula i Z C wherein Z denotes a -COO-alkyl radical with 1-5 carbonatoms in the alkyl group, a -COO-aryl or -'COOH radical and thecorresponding salts, such as alkali metal salts or ammonium salts orsalts with tertiary bases. As examples there may be mentioned:trimellitic acid anhydride, the Na salt of trimellitic acid anhydride,the ammonium salt of trimellitic acid anhydride, trimellitic acidanhydride monomethyl, monoethyl, monoisopropyl, mono-sec.-butyl ormono-tert.-butyl and monoisopentyl ester and trimellitic acid anhydridebenzoic acid ester. y

In these cases, a prepolymer possessing amino end groups is firstprepared by reaction of a tricarboxylic acid derivative of this typewith an excess of a diamine according to the definition, after which theprepolymer is allowed to react with at least 2 mols of a dicarboxylicacid dichloride, tricarboxylic acid anhydride-chloride ortetracarboxylic acid dianhydride.

Polymers corresponding to the formula [lb and having terminal acidgroups can be manufactured analogously by allowing a homopolymer,copolymer or block copolymer possessing amino end groups, for example apolyamide homopolymer, to react with at least 2 mols of anothercarboxylic acid derivative, for example a tricarboxylic acidanhydride-chloride, such as trimellitic acid l,2-anhydride-chloride.

Block copolymers with terminal acid groups can be obtained by reactingan excess of one or more copolymers or homopolymers with terminal acidgroups, prepared in the manner described above, with homopolymers orcopolymers possessing amino end groups.

Finally, starting products corresponding to the formula ll, havingterminal acid groups and a partially block-like arrangement ofpolyamide, polyamide-acid and/or polyamide-amide-acid units, can beprepared, for example, by reacting an excess of a homopolymer possessingterminal acid groups with a diamine according to the definition.

Polymers of the formula V possessing amino end groups can bemanufactured analogously by employing the diamine or diamines or thepolymers with terminal amino groups in excess over the carboxylic acidderivatives or the polymers possessing terminal acid groups.

Polyamide-acid or polyamide-amide-acid polymers thus obtained can, ifdesired, by cyclised thermally or chemically, by methods which are inthemselves known, before the reaction with the aminosilanes of theformula III or the compounds of the formula IV.

Preferred dicarboxylic acid derivatives, tricarboxylic acid derivativesor tetracarboxylic acid derivatives for the above reactions areisophthalic acid dichloride, trimellitic acid anhydride, trimelliticacid l,2-anhydride-chloride, pyromellitic acid dianhydride andbenzophenonetetracarboxylic acid dianhydride.

Compounds which are in themselves known can be used as the diamines ofthe formula H N-R -NH The following may be mentioned as specificexamples of carbocyclic-aromatic diamines: o-, m and p-phenylenediamine,diaminotoluenes, such as 2,4- diaminotoluene,l,4-diamino-2-methoxybenzene, 2,5-

diaminoxylene, l,3-diamino-4-chlorobenzene, l ,4 diamino-Z,S-dichlorobenzene, 1,4-diamino-2-bromobenzene,l,3-diamino-4-isopropylbenzene, N,N

diphenyl- 1,4-phenylenediamine, 4,4'-diaminodiphenyl-2,2-propane,4,4'-diaminodiphenylmethane, 2,2'- or 4,4'-diarninostilbene,4,4-diaminodiphenyl-ether, 4,4'-diaminodiphenyl-thioether,4,4'-diaminodiphenylsulphone, 3,3'-diaminodiphenylsulphone, 4,4'-diaminobenzoic acid phenyl ester, 2,2'- or 4,4'- diaminobenzophenone,4,4-diaminobenzil, 4-(4'- aminophe nylcarbamoyl )-aniline, bis-(4-aminophenyl phosphine oxide, bis-(4-aminophenyl)-methylphosphineoxide, bis-(3-aminophenyl)-methylphosphine oxide,bis-(4-aminophenyl)-phenylphosphine oxide,bis-(4-aminophenyl)-cyclohexylphosphine oxide, N,N-bis-(4-aminophenyl)-N-phenylamine, N,N-bis-(4- aminophenyl)-N-methylamine, 4,4'-diaminodiphenylurea, 1,8- or1,5-diaminonaphthalene, 1,5- diaminoanthraquinone, diaminofluoranthene,bis-(4- aminophenyl)-diethylsilane, bis-(4-aminophenyl)- dimethylsilaneand bis-(4-aminophenyl)-tetramethyldisiloxane.

Particularly preferred compounds are 1,4- and above all1,3-phenylenediamine, 4,4'-diaminodiphenyl ether and4,4-diaminodiphenyl-methane.

Examples of heterocyclic diamines are: 2,6- diaminopyridine,2,4-diaminopyrimidine, 2,4-diaminos-triazine, 2,7-diamino-dibenzofurane,2,7-diaminocarbazole, 3,7-diaminophenothiazine and 2,5-diamino-1,3,4-thiadiazole.

As aliphatic diamines there may be mentioned: dimethylenediamine,trimethylenediamine, tetramethylenediamine, hexamethylenediamine,heptamethylenediamine, octamethylenediamine, nonamethylenediamine anddecamethylenediamine, 2,2-dimethylpropylenediamine,2,5-dimethylhexamethylenediamine, 2,5-dimethylheptamethylenediamine,4,4-dimethylheptamethylenediamine, 3-methylheptamethylenediamine,3-methoxyhexamethylenediamine, S-methylnonamethylenediamine, 2,1l-diaminododecane, 1,1 2-diaminooctadecane, 1 ,2-bis-(3-aminoprpoxy)-ethane, N,N'-dimethylethylenediamine,N,N-diethyl-l,3-diaminopropane and N,N-dimethyl- 1,6-diaminohexane aswell as the diamines of the fordiaminodicyclohexylmethane may bementioned as suitable cycloaliphatic diamines and l,4-bis-( 2-methyl4-aminopentyl )-benzene, l,4-bis-( l l-dimethyl-S- aminopentyl)-benzeneand 1,3- or 1,4-bis-(aminomethyl)-benzene may be mentioned as suitablearaliphatic diamines.

The condensation reactions described can be carried out in a mannerwhich is in itself known, preferably in an anhydrous organic solvent,for example N,N-dialkylamides of monocarboxylic acids with 1-4 carbonatoms, such as N,N-dimethylacetamide and N,N-dimethylformamide;N-methyl-Z-pyrrolidone, N,N,N',N- tetramethylurea, tetrahydrofurane,cyclohexanone, hexamethylphosphoric acid triamide (Hexametapol),tetrahydrothiophene dioxide (sulpholane) or dimethylsulphoxide.Depending on the nature of the reactants, the reaction temperatures arebetween about C and +250C.

The aminosilanes of the formula III, according to the definition, arealso known in themselves or can be manufactured according to knownmethods.

The following may be mentioned as examples of suitable aminosilanes ofthe formula III; aminomethyldi-n-propoxymethylsilane,(,B-aminoethyD-di-npropoxy-methylsilane,(B-aminoethyD-diethoxyphenylsilane, (B-aminoethyl)-tri-n-propoxysilane,(B- aminoethyl)-dimethoxy-methylsilane,(y-aminopropyl)-di-n-propoxy-methylsilane, (y-aminopropyD-di-n-butoxy-methyl-silane, ('y-aminopropyl)-trimethoxysilane,('y-aminopropyl)-triethoxysilane,(y-aminopropyl)-di-n-pentoxy-phenylsilane, ('y-aminopropyU-methoxy-n-propoxy-methylsilane, (S-aminobutyl dimethoxy-methylsilane,(3-aminophenyl)-di-npropoxy-methylsilane,(4-amin0phenyl)-tri-n-propoxysilane, [B-( 4-aminophenyl )-ethyl-diethoxy-methylsilane, [,B-( 3-aminophenyl)-ethyl]-di-n-propoxy-phenylsilane,['y-(4-aminophenyl)-propyl]-di-n-propoxymethylsilane,['y-(4-aminophenoxy)-propyl]-di-npropoxymethylsilane and [y-(3-aminophenoxypropyl]-di-n-butoxymethylsilane. ('y-AminopropyD-triethoxysilane and['y-(4-aminophenyl)-propyl]-di-npropoxy-methylsilane, but veryparticularly (y-aminopropyl)-di-n-propoxy-methylsilane and [y-(amino- 12phenoxy)-propyl]-di-n-propoxy-methylsilane, are preferred.

The compounds of the formula IV are new; they can be manufactured inwhat is in itself a conventional manner by reaction of aminosilanes ofthe formula III with a tricarboxylic acid anhydride-chloride ortetracarboxylic acid dianhydride of the formula a R \o wherein R has themeaning indicated under the formula I, p is the number 1 or 2, 2;;together with Z if p 2, forms an anhydride group or Z if p 1, representsthe COCl radical, with Z and Z being in the ortho-position to oneanother and the anhydride group being bonded to adjacent carbon atoms ofthe radical R such as pyromellitic acid dianhydride andbenzophenonetetracarboxylic acid dianhydride, but above all trimelliticacid 1,2-anhydride-chloride. The reaction is preferably carried out inan anhydrous organic solvent, such as chlorinated aliphatichydrocarbons, for example dichloroethane, methylene chloride orperchloroethylene, and in the presence of an acidbinding agent, such astriethylamine, at temperatures of about 40C to +30C. After completion ofthe reaction, and after filtering off the hydrochloride which hasprecipitated, the compounds of the formula IV can be purified byrecrystallization from a suitable solvent, such as benzene.

Examples of suitable compounds of the fonnula IV are: trimellitic acidl,Z-anhydride-B-(trimethoxysilyl)- ethylamide, trimellitic acid1,2-anhydn'de-y-(di-npropoxy-methylsilyl)-propylarnide, trimellitic acid1,2- anhydride-y-(tri-n-pr0poxysilyl)-propylamide, trimellitic acid 1,2-anhydride-4-[y-(di-n-propoxy-methylsilyl)-propoxy]-anilide,trimellitic acid 1,2-anhydride-4'-['y-(di-n-propoxy-methylsilyl)-propyl]-anilide, trimellitic acid 1,2-anhydride-3 '-(diethoxy-methylsilyl anilide, pyromellitic acid1,2-anhydride-4-[B-(trimethoxysilyl)-ethylamide], pyromellitic acid1,2-anhydride-4-[7-(di-n-propoxymethylsilyl)-propylamide] andbenzophenonetetracarboxylic acid 3,4-anhydride-4'-[y-(triethoxysilyl)-propylamide].

' The reaction of the abovementioned starting products with at least 2mols of an aminosilane of the formula III or of a compound of theformula IV, can be carried out in a manner which is in itself known,preferably in an anhydrous organic solvent at temperatures between about20C and +50C, especially about lC to +25C. Suitable organic solventsare: N,N- dimethylacetamide, N,N-diethylacetamide,N,N-dimethylformamide, N,N-dimethylmethoxyacetamide, N-methyI-Z-pyrrolidone, N-acetyl-2-pyrrolidone, methyl-e-caprolactam,hexamethylphosphoric acid triamide (Hexametapol),N,N,N,N-tetramethylurea, tetrahydrofurane, cyclohexanone,tetrahydrothiophene dioxide (sulpholane) and dimethylsulphoxide.

The reaction can also be carried out in mixtures of such solvents. Onthe other hand it is also possible to dilute these preferred solventsystems with other organic aprotic solvents, such as aromatic,cycloaliphatic or aliphatic, optionally chlorinated, hydrocarbons, forexample benzene, toluene, xylenes, cyclohexane, pentane, hexane,petroleum ether and methylene chloride or dioxane.

If the aminosilanes of the formula III and/or the compounds of theformula IV are reacted with polymers according to the definition, thelatter are suitably employed in the form of their solutions as obtainedwhen the polymers are manufactured.

In the reaction with aminosilanes of the formula III or compounds of theformula IV, preferably at least 2 mols of the same aminosilane of theformula III or the same compound of the formula IV are used. However, tomanufacture asymmetrical prepolymers of the formula I it is alsopossible to employ mixtures of the said compounds in corresponding molaramounts or to carry out the reaction stepwise with in each case at leastone mol of a different aminosilane of the formula HI or of a differentcompound of the formula IV.

In all these cases, the aminosilane or the compound of the formula IV ispreferably employed in the stoichiometric amount.

A possible cyclisation of the prepolymers which can be used according tothe invention, of the polyamideacid or polyamide-amide-acid category, tothe corresponding polyimides or polyamide-imides, by a chemical methodprior to the thermal crosslinking, is also carried out in a manner whichis in itself known, for example by gentle treatment with a dehydratingagent, used by itself or mixed with a tertiary amine; examples of agentswhich can be used are acetic anhydride, propionic anhydride anddicyclohexylcarbodiimide or a mixture of acetic anhydride andtriethylamine or pyridine. To avoid premature crosslinking, the reactionshould be carried out at temperatures which are as low as possible,preferably at a temperature below 50C and in particular between about20C and +25C. In general, however, such a chemical cyclisation precedingthe crosslinking will be dispensed with.

The crosslinked polymers containing siloxane groups, according to theinvention, are insoluble in organic solvents; they are distinguished bygood mechanical, electrical and thermal properties, especially by goodheat stability and good mechanical properties at low temperatures.

The crosslinking of the prepolymers is usually carried out during theconversion of the latter to industrial products, such as fibres, thinand thick films, coatings, foams, laminating resins, laminates,compression moulding powders, compression mouldings and the like. At thesame time, customary additivies, such as pigments, fillers and the like,can also be added to the prepolymers. Non-cyclised prepolymers which canbe used according to the invention, with a or a l0,

above all a or a 5, are, because of their good processability attemperatures around 160C, above all suitable for the manufacture oflaminates, foams and compression mouldings. The present inventiontherefore also relates to the use of polymers containing siloxanegroups, which have been crosslinked in accordance with the invention, asindustrial products, especially as laminates, foams or compressionmouldings, if a or a 10.

EXAMPLE 1 13.553 g (0.0666 mol) of isophthalic acid dichloride aredissolved in ml of anhydrous N,N-dimethylacetamide (DMA) at l5C undernitrogen in a 750 ml sulphonation flask which is equipped with astirrer, internal thermometer, dropping funnel and gas inlet tube.3.6047 g (0.0333 mol) of m-phenylenediamine in solid form are introducedinto this solution at 10 to l5C, whilst cooling. After the exothermicreaction has subsided, the mixture is stirred for a further 2 hours at0-5C and a solution of 6.746 g (0.0666 mol) of triethylamine in 50 ofanhydrous DMA is then added dropwise at the same temperature. Afterstirring for 1 hour at 05C, a solution of 14.6266 g (0.0666 mol) of(y-aminopropyl)-di-n-propoxymethylsilane and 6.746 g (0.0666 mol) oftriethylamine in 50 ml of anhydrous DMA is added dropwise to thesuspension obtained. The reaction mixture is then stirred for 2 hours atroom temperature (2025C) and the triethylamine hydrochloride which hasprecipitated is filtered off through a glass frit and rinsed 3 timeswith a total of 80 ml of anhydrous DMA. A slightly viscous solution of apolyamide prepolymer with terminal methyl-di-n-propoxysilyl groups andan average molecular weight (M) of approx. 800 is obtained; 1;,-,,,,0.07 dl/g (0.5 percent in DMA at 25C).

The solution of the above prepolymer is poured onto an aluminium foiland heated as follows: For 3 hours to 70C/ 30 mm Hg, for 3 hours to ll0C/30 mm Hg, for 10 hours to C/ 30 mm Hg and finally for 4 hours to200C/0.l mm Hg. A clear, mechanically firm coating of the correspondingcrosslinked polyamide containing siloxane groups, having a siliconcontent of 9.3 percent by weight, is obtained. If the aluminium foil isdissolved off with dilute hydrochloric acid, a clear, colourless film ofgood mechanical strength is obtained.

EXAMPLE 2 Following the procedure described in Example 1, 4.866 g (0.045mol) of m-phenylenediamine in anhydrous DMA, with the addition of 8.096g (0.08 mol) of triethylamine, are reacted with 8.121 g (0.04 mol) ofisophthalic acid dichloride. A solution of a polyamide block withterminal amino groups and an average molecular weight of approx. 2,000is obtained. This solution is added dropwise over the course of 15minutes, at 20-25C, to a solution of 4.856 g (0.01 mol) of trimelliticacid l,2-anhydride-4'[y-di-n-propoxy-methylsilyl)-propoxy]-anilide ofthe formula A solution of a polyamide prepolymer with terminal methyldi-n-propoxysilyl groups and an average molecular weight of approx.3,000 results; 17,- 0.19 dl/g (0.5 percent in DMA at 25C).

After suitable dilution, this solution is converted, in the mannerdescribed in Example 1, to coatings or films of the correspondingcrosslinked polyamide; silicon content 1.9 percent by weight.

The trimellitic acid1,2-anhydride-4-['y-(di-npropoxymethylsilyl)-propoxy]-anilide used inthe above example can be prepared as follows:

50 ml of dichloroethane are initially introduced into a 1.5 lsulphonation flask which is equipped with a stirrer, internalthermometer, reflux condenser, 2 dropping funnels with pressureequilibration, and a nitrogen inlet, and are cooled to 30 to 40C. 21.0 g(0.1 mol) of trimellitic acid 1,2-anhydride-chloride in 250 ml ofdichloroethane and 31.1 g (0.1 mol) of[y-(4-aminophenoxy)-propyl]-di-n-propoxy-methylsilane and 10. l g oftriethylamine in 250 ml of dichloroethane are then simultaneously addeddropwise at 30C over the course of 1 hour and 20 minutes. The reactionmixture is stirred for approx. 4 hours at 30C, after which it is allowedto warm to room temperature. The triethylamine hydrochloride which hasprecipitated is filtered off under nitrogen and the filtrate isevaporated to dryness in vacuo, with exclusion of moisture. Theresulting yellow crystalline powder is recrystallised 3-4 times frombenzene, with exclusion of moisture, to remove residual triethylaminehydrochloride. Yield 38 g (76 percent of theory).

EXAMPLE 3 Analogously to the procedure described in Example 1, 10.814 g(0.1 mol) of m-phenylenediamine are dissolved in 100 ml of anhydrousDMA. 16.264 g (0.08 mol) of isophthalic acid dichloride in solid formare introduced into the resulting solution at 20C, whilst cooling. Thereaction mixture is then stirred for 2 hours at 5C and a solution of16.192 g (0.16 mol) of triethylamine in 50 ml of dry DMA is then addeddropwise. After stirring for one hour at 510C, the solution is cooled to30C and a solution of 8.4232 g (0.04 mol) of trimellitic acid1,2-anhydride-chloride in 60 ml of 1,2-dichloroethane is added dropwiseat this temperature. The reaction mixture is then kept at 20C for 20minutes, followed by 60 minutes at 510C, and finally a solution of 4.048g (0.04 mol) of triethylamine in 50 ml of anhydrous DMA is addeddropwise. After stirring the reaction mixture for a further hour, at20C, the triethylamine hydrochloride is filtered off through a glassfrit and carefully rinsed three times with DMA. A solution of 8.776 g(0.04 mol) of (yaminopropyl)-di-n-propoxy-methylsilane in 50 ml of DMAis introduced over the course of 10 minutes into the solution of thepolyamide block with terminal anhydride groups (average molecular weightapprox. 1,400) obtained above, at l520C. After stirring for 2 hours atroom temperature (25C), a solution of a polyamide prepolymer withterminal methyl-di-n-propoxysilyl groups and an average molecular weightof approx. 1,850 is obtained; 1;,-,,,, 0.1 1 dl/g (0.5% in DMA at C).This solution is made up to a total of 440 g with anhydrous DMA and 22 g(0.001 mol) of the resulting diluted solution are converted, in themanner described in Example 1, to coatings or films of the 16corresponding crosslinked polyamide, having good thermal and mechanicalproperties; silicon content: 3.2 percent by weight.

EXAMPLE 4 Analogously to Example 3, 21.628 g (0.2 mol) ofmphenylenediamine, 32.528 g (0.16 mol) of isophthalic acid dichlorideand 32.4 g (0.32 mol) of triethylamine are first reacted with 16.830 g(0.08 mol) of trimellitic acid 1,2-anhydride-chloride to give apolyamide block with anhydride end groups and subsequently with 24.920 g(0.08 mol) of [y-(4-aminophenoxy)-propyl]-di-n-propoxy-methylsilane togive a polyamide prepolymer with terminal methyl-di-npropoxysilylgroups; average molecular weight approx. 2,000. The resulting solutionis made up to a total of 727 g with anhydrous DMA, and 36.34 g (0.002mol) of the resulting diluted solution are converted, in the mannerdescribed, to coatings or films of the corresponding crosslinkedpolyamide; silicon content: 2.9 percent by weight.

EXAMPLE 5 26.5 g (0.082 mol) of finely powdered3,3,4,4-benzophenonetetracarboxylic acid dianhydride are sus pended in50 ml of anhydrous DMA under a nitrogen atmosphere in a 350 mlsulphonation flask which is equipped with a stirrer, dropping funnel andinternal thermometer. A solution of 8.15 g (0.041 mol) of 4,4-diaminodiphenylmethane in 34 ml of anhydrous DMA is added dropwise tothe resulting suspension over the course of 30 minutes whilst stirringat 1015C, and the reaction mixture is then stirred for 2 hours at roomtemperature (2025C). The resulting solution is cooled to 05C;thereafter, 25.6 g (0.082 mol) of[y-(4-aminophenoxy)-propyl]-di-n-propoxy-methylsilane are added dropwiseat this temperature over the course of 30 minutes. The solution is thenstirred for one hour at room temperature. In this way, a 43 percentstrength solution of a polyamide-acid prepolymer is obtained, which hasa viscosity of 300 centipoises at room temperature. m of the prepolymer0.083 dl/g (0.5 percent in DMA at 25C).

Glassfibre fabric (for example E-glass with an aminosilane finish) isimpregnated with this solution by drawing the fabric once through thepolymer solution. The impregnated fabric is dried for one hour at50C/200 mmmHg and for one hour at 50"C/10 mm Hg. Several of the prepregsthus obtained are stacked above one another and pressed in a platenpress at 165C, for 5 minutes under contact pressure and for 7 hoursunder a pressure of 500 kp/crn to give laminates. The pressure isperiodically released during the first hour in order to facilitate theremoval of volatile products. The laminates are then post-cured for 16hours at 200C/20 mm Hg. After complete curing, the resin content of thelaminates is 20 percent by weight (determined by ashing). Well-bonded,bubblefree laminates of good heat stability and excellent mechanical andelectrical properties are obtained.

EXAMPLE 6 Analogously to the procedure described in Example 5, 64.45 g(0.2 mol) of finely powdered 3,3,4,4-benzophenonetetracarboxylic aciddianhydride are reacted with 20.03 g (0.1 mol) of4,4-diaminodiphenyl-ether and 62.30 g (0.2 mol) of ['y-(4-aminophenoxy)-propyl]-di-n-propoxy-methylsilane in 240 ml of anhy- EXAMPLE 7 Followingthe procedure described in Example 5, 26.5 g (0.082 mol) of3,3,4,4-benzophenonetetracarboxylic acid dianhydride in 84 ml ofanhydrous DMA are reacted with 8.15 g (0.041 mol) of4,4'-diaminodiphenylmethane. The resulting solution of thepolyamide-acid block possessing anhydride end groups is then treatedwith 18.0 g (0.082 mol) of (y-arninopropyl)-di-n-propoxy-methylsilane atO5C and the mixture is stirred for one hour at room temperature. A 40percent strength solution of a polyamide-acid prepolymer which has aviscosity of 300 centipoise at 25C is obtained and is converted, in themanner described in Example 5, to laminates of the correspondingcrosslinked polyimide. 1;,-,,,, of the prepolymer 0.086 dl/g (0.5percent in DMA at 25C). The laminates show good mechanical propertieseven at low temperatures.

EXAMPLE 8 26.5 g (0.082 mol) of 3,3',4,4-benzophenonetetracarboxylicacid dianhydride in 130 ml of anhydrous tetrahydrofurane are heatedunder reflux in a nitrogen atmosphere in a 750 ml sulphonation flaskequipped with a stirrer, dropping funnel and internal thermometer.

A solution of 8.15 g (0.041 mol) of 4,4-diaminodiphenylmethane in 72 mlof anhydrous tetrahydrofurane is added dropwise to the resultingsuspension over the course of 30 minutes whilst stirring under refluxand the reaction mixture is then kept under reflux for a further hour.The resulting solution is cooled to O5C. At this temperature, 25.6 g(0.082 mol) of [y-(4- aminophenoxy)-propyl]-di-n-propoxy-methylsilaneare added dropwise over the course of 15 minutes and the mixture isstirred for a further hour at 5C. A 25 percent strength solution of apolyamide-acid prepolymer having an average molecular weight of approx.1,500 is obtained.

Glassfibre fabric is impregnated with this prepolymer solution in themanner described in Example 5, but the fabric is merely dried for onehour at 50C/200 mm Hg. The production of laminates by pressing theprepregs thus obtained is carried out in the manner indicated in Example5. Firmly bonded, bubble-free laminates of the corresponding crosslinkedpolyimide, having a resin content of 19 percent by weight, are obtained.

The laminates show good mechanical and thermal properties.

EXAMPLE 9 26.5 g (0.082 mol) of 3,3',4,4-benzophenonetetracarboxylicacid dianhydride in 40 g of anhydrous cyclohexanone are heated underreflux in a nitrogen atmosphere in a 350 ml sulphonation flask of thetype described. A solution of'8l5 g (0.041 mol) of 4,4-diaminodiphenylmethane in 39 g of anhydrous cyclohexanone is addeddropwise to the resulting suspension over the course of 30 minuteswhilst stirring under reflux. The resulting solution is .stirred for afurther hour at room temperature and is then cooled to C.

At this temperature, 2.56 g (0.082 mol) of [y-(4-aminophenoxy)-propyl]di-npropoxy-methylsilane are added dropwise overthe course of 15 minutes and the reaction mixture is stirred for afurther half hour. A 40 percent strength solution of a polyamide-acidprepolymer having methyl-di-n-propoxysilyl end groups and possessing anaverage molecular weight of approx. 1,500 is obtained.

This solution is coverted, in the manner described in the precedingExample 5, to a glassflbre laminate of the corresponding crosslinkedpolyimide. Firmly bonded, bubble-free laminates of good flexuralstrength and heat stability are obtained.

EXAMPLE 10 4.06 g (0.02 mol) of isophthalic acid dichloride aredissolved in 25 ml of anhydrous DMA under nitrogen at l5C. 1.08 g (0.01mol) of pulverulent mphenylenediamine are added in portions whilststirring and the reaction mixture is stirred for 1 hour at 0C. Asolution of 2.02 g (0.02 mol) of triethylamine in 7 ml of anhydrous DMAis then added dropwise at this temper- 'ature and the mixture is stirredfor a further hour, Fi-

nally, a solution of 4.4 g (0.02 mol) of(y-aminopropyl)-di-n-propoxy-methylsilane and 2.02 g (0.02 mol) oftriethylamine in 7 ml of anhydrous DMA is added dropwise and thereaction mixture is stirred for 2 hours at room temperature. Thetriethylamine hydrochloride which has precipitated is filtered off. Aclear solution of the prepolymer is obtained.

This solution is completely evaporated to dryness in vacuo at 60C. Theresulting dry compression moulding powder is compression moulded to givesheets by the compression moulding process at C under a pressure of 200kp/cm For postcuring, the sheets are heated to 200"C/10 mm Hg for 16hours. Transparent sheets having a silicon content of 9.1 percent byweight are obtained.

EXAMPLE 1 l 8.12 g (0.04 mol) of isophthalic acid dichloride aredissolved in 60 ml of anhydrous DMA at l 5C under nitrogen in a 200 mlsulphonation flask equipped with a stirrer, dropping funnel andintemalthermometer. A solution of 17.5 g (0.08 mol) of(y-aminopropyD-di-npropoxy-methylsilane and 8.08 g (0.08 mol) oftriethylamine in 40 ml of anhydrous DMA is added dropwise thereto at atemperature of 10C to l5C, whilst stirring. The reaction mixture is thenstirred for 2 hours at 0C to 5C and then for a further 2 hours at roomtemperature (20-25C). After filtering off the triethylaminehydrochloride, which has precipitated, on a glass frit, a solution ofthe prepolymer (a o) is obtained.

m of the prepolymer 0.04 dl/g (0.5 percent in DMA at 25C).

Glassfibre fabric is impregnated by dipping it in the resultingprepolymer solution. The impregnated fabric' is then briefly dried in avacuum drying cabinet at 50C/300 mm Hg. This operation is repeated 7more times in order to apply sufficient resin to the fabric. The fabricis then dried for one hour at 50C/300 mm Hg and for 1 hour at 50C/10 mmHg. Several of the dried prepregs thus obtained are stacked above oneanother, pressed in a platen press at 165C under a pressure of 400 kp/cmfor 7 hours and then post-cured for 16 hours at 200C/10 mm Hg. Alaminate of good bond strength is obtained.

EXAMPLE 12 12.9 g (0.04 mol) of finely powdered3,3,4,4-benzophenonetetracarboxylic acid dianhydride are suspended in 50ml of anhydrous DMA under nitrogen in a 200 ml sulphonation flask whichis equipped with a stirrer, dropping funnel and internal thermometer.The reaction mixture is cooled to O5C and 17.5 g (0.08 mol) of(y-aminopropyl)-di-n-propoxy-methylsilane are then added dropwise,whilst stirring. After stirring the reaction mixture for one hour atroom temperature, a clear solution of the prepolymer (a is produced; "nof the prepolymer 0.044 dl/g (0.5 percent in DMA at 25C).

Glassfibre fabric is impregnated with this solution in the mannerdescribed in Example 10, and converted to prepregs and finally tolaminates.

EXAMPLES l3 16 A solution of 10.01 g (0.05 mol) of4,4-diaminodiphenylether (II) in 60 ml of anhydrous DMA is addeddropwise over the course of 15 minutes to a solution of 13.08 g (0.06mol) of pyromellitic acid dianhydride (PMDA; I), in 40 ml of anhydrousDMA under nitrogen at between 20 and 30C in an apparatus of the typedescribed in Example 5, and after completion of the addition the mixtureis further stirred at room temperature for about 1 hour. A solution of6.4 g (0.022 mol) of (y-aminopropyl)-di-n-propoxy-methylsilane (III) inml of DMA is then added dropwise at room temperature and the reactionmixture is stirred for a further hour. A clear, yellowcoloured, approx.25 percent strength solution of a polyamide-acid prepolymer of the aboveformula having two silicon-functional end groups and an average value ofa 5 is thus obtained, the solution having a viscosity of approx. 60centipoise at 20C; n,-,,,, of the prepolymer 0.21 dl/g (0.5% in DMA at25C).

The prepolymer' solutions listed in the table below 20 Films withsimilar properties can be obtained if, in the above examples, thepyromellitic acid dianhydride is replaced, for example by correspondingamounts of benzophenonetetracarboxylic acid dianhydride, and the4,4-diaminodiphenyl-ether is replaced by corresponding amounts of4,4-diaminodiphenylmethane.

EXAMPLE 17 32.22 g (0.1 mol) of finely powdered3,3',4,4'-benzophenonetetracarboxylic acid dianhydride are dissolved in120 ml of anhydrous DMA under nitrogen in an apparatus of the typedescribed in Example 1. A solution of 9.91 g (0.05 mol) of4,4'-diaminodiphenylmethane in 80 ml of DMA is added dropwise at 1015Cin such a way that the temperature of the reaction solution does notexceed 15C. The reaction solution is then stirred for 2 hours at approx.25 C. The solution is then cooled to O5C and at this temperature asolution of 31.15 g (0.1 mol) of['y-(4-aminophenoxy)-propyl]-di-n-propoxy-methylsilane in 35 ml ofanhydrous DMA is added dropwise. Finally, the reaction solution isstirred for a further hour at approx. 25C.

A mixture of 90 ml of acetic anhydride and 60 ml of pyridine is addeddropwise to this solution whilst stirring and the mixture is stirred fora further 16 hours. A voluminous precipitate forms. The reaction mixtureis poured into a large excess of water whilst stirring vigorously andthe product which has precipitated is filtered off, washed with waterand dried for 24 hours at C/100 mm Hg and for 24 hours at 50C/10 mm Hg.After grinding in a ball mill, the imidised (cyclised) prepolymer isobtained as a fine yellow powder.

This powder is introduced into a compression mould, heated to 300C, forcircular discs, and is heated under contact pressure for 3 minutes withrepeated venting. The pressure is then raised stepwise to 325 kp/cm andis maintained thereat for 1 hour at 300C. After release from the mouldat 220C, transparent discs of good are prepared analogously usingreactants I, II and III. 40 flexural. strength and good electricalproperties are Table Exam- PMDA I II III Viscosity of a (avern,,,,,(0.5% ple No. g mol g mol g mol the solution, age) in DMA centipoise 1411.99 0.055 10.01 0.05 2.19 0.01 approx. 200 10 0.38 dl/g 15 11.45 0.05210.01 0.05 1.45 0.005 approx. 1,800 25 0.60 dl/g 16 11.27 0.0516 10.010.05 0.98 0.0034 approx. 2,500 30 0.73 dl/g Films were cast from theabove prepolymer solutions obtained. both on lass lates and on aluminumsheetsafter g p EXAMPLE 18 stripping off the solvent, these films wereconverted into crosslinked siloxane-containing polyimide films byheating to 220C for 2 hours and subsequently heating to 250C for onehour. The resulting crosslinked films are insoluble even in stronglypolar organic solvents. Silicon contents of the films:

For a 5 approx. 2.0 percent by weight For a 10 approx. 1.2 percent byweight For a 25 approx. 0.7 percent by weight For a 30 approx. 0.5percent by weight.

These siloxane-modified polyimide films display exceptionally highadhesion to glass and metal surfaces and cannot be detached mechanicallyfrom the latter. By dissolving off the aluminum base with HCl,unsupported films can be obtained which in addition to very good heatstability and excellent electrical properties, exhibit good mechanicalstrengths and high elasticity.

EXAMPLE l9 Analogously to the procedure described in Example 5, 25.78(0.08 mol) of 3,3',4,4-benzophenonetetracarboxylic acid dianhydride,7.94 g (0.04 mol) of 21 4,4-diaminodiphenylmethane and 17.70 g (0.08mol) of ('y-aminopropyl)-triethoxysilane are reacted in 82 ml ofanhydrous DMA. A 40 percent strength Solution of a polyamide-acidprepolymer is obtained; n,,,,, of the prepolymer 0.08 dl/g (0.5 percentin DMA at 25C). Using this solution, prepregs are prepared in the mannerdescribed in Example and are pressed to give laminates.

EXAMPLE 20 Analogously to the procedure described in Example 5, 17.45 g(0.08 mol) of pyromellitic acid dianhydride, 7.94 g (0.04 mol) of4,4diaminodiphenyl-ether and 17.54 g (0.08 mol) of('y-aminopropyl)-di-n-propoxymethylsilane are reacted in 79 ml ofanhydrous DMA. A 31 percent strength solution of a polyamide acidprepolymer is obtained. m of the prepolymer 0.09 dl/g (0.5 percent inDMA at 25C).

Using this prepolymer solution, prepregs are prepared in the mannerdescribed in Example 5 and are subsequently pressed to give a laminatewith good mechanical and electrical properties.

EXAMPLE 21 5.26 g (0.025 mol) of trimellitic acid 1,2-anhydridechlorideare dissolved in 35 ml of anhydrous DMA at -l5C to 20C under nitrogen inan apparatus of the type described in Example 5. A solution of 2.48 g(0.0125 mol) of 4,4'-diaminodiphenylmethane and 2.53 g (0.025 mol) oftriethylamine in ml of anhydrous DMA is added dropwise to the solutionobtained, whilst cooling and stirring constantly, in such a way that thetemperature in the reaction vessel does not exceed -l5C. Aftercompletion of the addition, the mixture is stirred for a further 15minutes at the same temperature and a solution of 5.38 g (0.025 mol) of('y-aminopropyl)di-n-propoxymethylsilane in 6 ml of anhydrous DMA isthen added dropwise. Thereafter, the reaction mixture is stirred for 2hours at -25C and the triethylamine hydrochloride which has precipitatedis removed by filtration.

A mixture of 45 ml of acetic anhydride and 30 ml of pyridine is thenadded dropwise to the filtered solution, whilst stirring, and the wholeis stirred for a further 16 hours at room temperature. A fineprecipitate forms. The reaction mixture is poured into a large excess ofwater whilst stirring vigorously and the product which has precipitatedis filtered off, repeatedly rinsed with water and dried for 20 hours at50/100 mm Hg and for 20 hours at 50C/l0 mm Hg. After pulverising in amortar, the imidised prepolymer is obtained as a fine yellowish powder.

This powder is introduced into a compression mould for circular discswhich is heated to 300C and the powder is heated for 3 minutes undercontact pressure, with repeated venting. The pressure is then raisedstepwise to 900 kg/cm and this pressure is maintained at 300C for 1hour. After release from the mould at 220C, transparent discs of goodflexibility are ob tained; silicon content: 7.5 percent by weight.

The solution of the prepolymer, obtained in accordance with paragraph 1of the above example, can be used for the production of laminates asdescribed in the preceding examples. Laminates of good flexural strengthare obtained by impregnating glass fibres 5 times, brief drying at 50C/100 mm Hg and subsequent pressing of the prepregs at 150C/5 minutescontact pressure, 30 minutes at 125 kg/cm 30 minutes at 250 kp/cm and 6hours at 375 kg/cm and post-curing at 225C/10 mm Hg for 16 hours.

EXAMPLE 22 12.63 g (0.06 mol) of trimellitic acid 1,2-anhydridechlorideare dissolved in 60 ml of anhydrous DMA at 15C under nitrogen in anapparatus of the type described in Example 5. A solution of 26.32 g(0.12 mol) of ('y-aminopropyl)di-n-propoxy-methylsilane and 6.07 g (0.06mol) of triethylamine in 37 ml of anhydrous DMA is added dropwise tothis solution, whilst stirring, in such a way that the reactiontemperature does not exceed 15C. After completion of the addition, thereaction mixture is stirred for 1 hour at 0C and then for 1 hour at roomtemperature (2025C), after which the triethylamine hydrochloride whichhas precipitated is filtered off. A clear 30 percent strength solutionof a prepolymer is obtained.

Glass fibre fabric is impregnated with this prepolymer solution andbriefly dried in a vacuum drying cabinet at 50C/300 mm Hg. Thisoperation is repeated 7 more times in order to apply sufficient resin tothe fabric. The fabric is then dried for one hour at 50C/100 mm Hg andfor 1 hour at 50C/10 mm Hg. Several of the dried prepregs thus obtainedare stacked on top of one another and pressed in a platen press at C Cto give laminates.

EXAMPLE 23 5.28 g (0.0275 mol) of trimellitic acid anhydride and 10.91 g(0.055 mol) of 4,4diaminodiphenylmethane in 70 ml of N-methylpyrrolidoneare heated for 4 hours to 185C under nitrogen, whilst stirring. Aftercooling, the resulting solution is added dropwise to 17.73 g (0.055 mol)of 3,3,4,4benzophenonetetracarboxylic acid dianhydride in 50 ml ofN-methylpyrrolidone at 0C under nitrogen, whilst stirring. The reactionmixture is then stirred for 1 hour at room temperature and cooled to05C, and a solution of 12.07 g (0.055 mol) of(y-aminopropyl)-di-npropoxy-methylsilane in 10 ml of N-methylpyrrolidoneis added dropwise. The reaction mixture is then stirred for a furtherhour at room temperature. A 30 percent strength solution of apolyamide-imidepolyamide-acid. prepolymer is obtained, which isconverted to well-bonded laminates by impregnating twice, pressing theprepregs at C and post-curing at 225C. The prepolymer solution obtainedcan also be used, in accordance with the method described in Example 17,paragraphs 2 and 3, for the manufacture of mouldings by first preparinga compression moulding powder of the fully imidised prepolymer by using90 ml of acetic anhydride and 60 ml of pyridine and subsequentlycompression moulding this powder at 315C for 15 minutes, in the mannerindicated in Example 17, to give discs; silicon content: 4.1 percent byweight.

EXAMPLE 24 8.06 g (0.025 mol) of 3,3',4,4'-benzophenonetetracarboxylicacid dianhydride and 5.26 g (0.025 mol) of trimellitic acid1,2-anhydride-chloride are introduced into 45 ml of anhydrous DMA at 15Cunder nitrogen in an apparatus of the type described in Example 5. Asolution of 4.96 g (0.025 mol) of 4,4- diaminodiphenylmethane and 2.53 g(0.025 mol) of triethylamine in 15 ml of anhydrous DMA is added dropwisethereto, whilst stirring, in such a way that the reaction temperaturedoes not exceed 15C. After completion of the addition and after stirringthe reaction mixture for 2 hours at this temperature, a solution of10.76 g (0.05 mol) of ('y-aminopropyD-di-npropoxy-methylsilane in 12 mlof anhydrous DMA is added dropwise. The reaction mixture is then stirredfor 2 hours at 2025C and the triethylamine hydrochloride which hasprecipitated is filtered off. A 30 percent strength solution of apolyamide-amide-acid prepolymer is obtained which can be converted tolaminates of good bond strength in the manner described in the precedingexamples, at temperatures between 130 and 165C.

EXAMPLE 25 Analogously to Example 24, 8.06 g (0.025 mol) of3,3,4,4benzophenonetetracarboxylic acid dianhydride, 5.26 g (0.025 mol)of trimellitic acid 1,2-anhydride-chloride, 4.96 g (0.025 mol) of4,4-diaminodiphenylmethane, 2.53 g (0.025 mol) of triethylamine and10.76 g (0.05 mol) of (y-aminopropyD-di-npropoxy-methylsilane arereacted in 82 ml of anhydrous DMA. After filtering off the triethylaminehydrochloride, a mixture of 90 ml of acetic anhydride and 60 ml ofpyridine is added dropwise to the reaction solution, whilst stirring,and the whole is stirred for 16 hours at 2025C. A precipitate forms. Thereaction mixture is then poured into a large excess of water, withvigorous stirring, and the product which has precipitated is filteredoff, repeatedly washed with water and dried for 20 hours at 50C/ 100 mmHg and for 20 hours at 50C/10 mm Hg. After pulverising, the imidisedprepolymer is obtained as a fine yellowish powder.

This powder is compression moulded in the manner described in Example21, paragraph 3, at 305C, to give transparent discs of good flexibility;silicon content: 6.4 percent by weight.

EXAMPLE 26 Analogously to Example 24, 9.159 g (0.0435 mol) oftrimellitic acid 1,2-anhydride-chloride, 9.48 g (0.0435 mol) ofpyromellitic acid dianhydride, 8.71 g (0.0435 mol) of4,4-diaminodiphenyl-ether, 4.40 g (0.0435 mol) of triethylamine and19.26 g (0.087 mol) of (yaminopropyl)-triethoxysilane are reacted in 130ml of anhydrous DMA. A solution of a polyamide-amideacid prepolymer isobtained, which is used, in the manner described, for laminating glassfibres.

EXAMPLE 27 4.34 g (0.0218) mol) of 4,4'-diaminodiphenylmethane and 1.66g (0.0164 mol) of triethylamine are dissolved in 50 ml of anhydrous DMAunder nitrogen in an apparatus of the type described in Example 5, andthe solution is cooled to 15C. 3.46 g (0.0164 mol) of trimellitic acid1,2-anhydride-chloride in powder form are added in portions to thissolution in such a way that the reaction temperature does not exceed15C. The reaction mixture is then stirred for 1 hour at 15C and for afurther hour at 2025C. The resulting solution is added dropwise to asolution of 2.2 g (0.0068 mol) of 3,3',4,4'-benzophenonetetracarboxylicacid dianhydride in 40 ml of anhydrous DMA at C, whilst stirring. Thereaction solution is stirred for a further hour at 2025C and then cooledto 05C, and a solution of 0.6 g (0.0027 mol) of('y-aminopropyD-di-npropoxy-methylsilane in ml of DMA is added. Thereaction solution is stirred for a further hour at 25C and thetriethylamine hydrochloride which 24 has precipitated is then filteredoff. A solution of a prepolymer with a block-like arrangement of thepolyamide-amide-acid units is obtained.

This solution is cast on aluminum sheets and spread to give a thinlayer. The sheets have beforehand been roughened mechanically andcleaned with acetone. The coated sheets are dried in a drying cabinetunder the following conditions: 16 hours at 50C/20 mm Hg, 30 minuteseach at C/20 mm Hg, C/2O mm Hg, C/20 mm Hg, C/20 mm Hg and C/20 mm Hgand finally 2 hours at C/20 mm Hg. The coatings are then postcured for 2hours at 230C/10 mm Hg. This gives bubble-free coatings which exhibitgood adhesion; silicon content: 0.82 percent by weight.

Films can also be produced from the above solution under analogousdrying conditions.

EXAMPLE 28 Analogously to the procedure described in Example 21,paragraph 1, 2.316 g (0.01 1 mol) of trimellitic acid1,2-anhydride-chloride, 3.544 g (0.01 1 mol) of 3,3,4-,4'benzophenonetetracarboxylic acid dianhydride, 3.965 g (0.020 mol) of4,4-diaminodiphenylmethane, 2.226 g (0.022 mol) of triethylamine and0.877 g (0.004 mol) of (y-aminopropyl)-di-n-propoxy-methylsilane arereacted in 102 ml of anhydrous DMA. After filtering off thetriethylamine hydrochloride, a clear solution of a polyamide-amide-acidprepolymer with a statistical distribution of the polyamide-amide-acidand polyamide-acid units is obtained.

Films are cast with this solution both on glass plates and on aluminumsheets. After stripping off the solvent in vacuo by heating for threehours at 70C, three hours at 1 10C and 3 hours at 150C and subsequentlyfor 4 hours at 250C, crosslinked polyamide-imide films containingsiloxane groups are obtained; silicon content: 1.2 percent by weight.

EXAMPLE 29 Analogously to the procedure described in Example 21,paragraph 1, 6.74 g (0.032 mol) of trimellitic acid1,2-anhydride-chloride, 5.95 g (0.030 mol) of 4,4-diaminodiphenylmethane, 3.24 g (0.032 mol) of triethylamine and 0.88 g(0.004 mol) of ('y-aminopropyD-din-propoxy-methylsilane are reacted in141 ml of anhydrous DMA. After filtering off the triethylaminehydrochloride, a clear solution of a polyamide-amide-acid prepolymer isobtained. which is converted into films and coatings in the mannerdescribed in the preceding examples. Silicon content: 0.96 percent byweight.

EXAMPLE 30 A. Preparation of a polyamide block with amino end groups2.812 g (0.026 mol) of m-phenylenediamine are dissolved in 50 ml ofanhydrous DMA under nitrogen in a 500 ml sulphonation flask equippedwith a stirrer, internal thermometer, dropping funnel and a nitrogeninlet tube. 4.872 g (0.024 mol) of isophthalic acid dichloride in solidform are added in portions to the resulting solution, whilst cooling to15C to 5C, and the reaction mixture is kept for one hour at 5C and thenfor 3 hours at 2025C. A solution of 4.84 g (0.048 mol) of triethylaminein 30 ml of anhydrous DMA is then added dropwise at 5l0C to neutralisethe hydrogen chloride produced. After stirring for one hour at roomtemperature, the triethylamine hydro- 25 chloride which has precipitatedis filtered off under nitrogen and the reaction product is washedcarefully three times with a little anhydrous DMA.

B. Preparation of a polyamide-acid block with anhydride end groups 9.02g (0.028 mol) of 3,3',4,4'-benzophenonetetracarboxylic acid dianhydrideare suspended in 65 ml of anhydrous DMA under nitrogen in an apparatusof the type described above. A solution of 4.806 g (0.024 mol) of4.4'-diaminodiphenyl-ether in 50 ml of anhydrous DMA is then addeddropwise at 20C. The reaction mixture is then stirred for 1 hour at2025C.

C. Preparation of a polyamide-polyamide-acid prepolymer The solutionobtained according to A) is added dropwise to the solution obtainedaccording to B) under nitrogen at 5l0C. Thereafter, the reaction mixtureis stirred for 1 hour at 2025C and is then cooled to O5C, and a solutionof 0.878 g (0.004 mol) of (yaminopropyl)-di-n-propoxy-methylsilane isadded dropwise. The resulting reaction solution is stirred for a furtherhour at 2025C. A solution of a polyamidepolyamide-acid block copolymeris obtained which is converted to films by casting and subsequent drying(1 hour at 80C and 1 hour at 150C, 2 hours at 220C and 1 hour at 250C);silicon content: 0.56 percent by weight.

EXAMPLE 31 A. Preparation of a polyamide block with amino end groupsAnalogously to the procedure described in Example 30 under A), 14.059 g(0.130 mol) of m-phenylenediamine, 24.364 g (0.12 mol) of isophthalicacid dichloride and 24.288 g (0.24 mol) of triethylamine are reacted in178 ml of anhydrous DMA to give a polyamide block with amino end groups.

B. Preparation of the prepolymer The solution obtained according to A)is added dropwise to a solution of 4.834 g (0.015 mol) of 3,3,',4,4'-benzophenonetetracarboxylic acid dianhydride in 163 ml of anhydrous DMAat 0C under nitrogen, whilst stirring. Thereafter, the resultingreaction solution is stirred for 1 hour at 2025C and then cooled to O5C,and a solution of 2.194 g (0.01 mol) of('yaminopropyl)din-propoxy-methylsilane in ml of anhydrous DMA is added.After stirring for a further hour at 25C, a prepolymer solution isobtained, with which films are produced in the manner described inExample 31; silicon content: 0.8 percent by weight.

It is also possible to prepare the imidised prepolymer as a fine powderfrom the above solution, using 120 ml of acetic anhydride and 80 ml ofpyridine, analogously to the procedure described in Example 17.

This powder is moulded by the compression process at 300320C to givesheets or bars of good flexural strength and good electrical properties.

EXAMPLE 32 A. Preparation of a polyamide block with amino end groupsAnalogously to the procedure described in Example 30 under A), 14.059 g(0.13 mol) of m-phenylenediamine, 24.364 g (0.12 mol) of isophthalicacid dichlo- 26 ride and 24.288 g (0.24 mol) of triethylamine arereacted in 176 ml of anhydrous DMA to give a polyamid block with aminoend groups.

B. Preparation of the prepolymer To the solution obtained according toA) are added, whilst stirring and under nitrogen, at 15C, first 0.404 g(0.004 mol) of triethylamine in 5 ml of DMA and then, in portions, amixture of 1.289 g (0.004 mol) of pulverule nt 3 ,3 ',4,4-benzophenonetetracarboxylic acid dianhydride and 0.842 g (0.004 mol) ofpulverulent trimellitic acid 1,2-anhydride-chloride. In the coursethereof, the reaction temperature should not exceed 15C. Aftercompletion of the addition, the reaction mixture is stirred first for 1hour at 15C and then for a further hour at 0C and thereafter a solutionof 1.878 g (0.004 mol) of trimellitic acid 1,2 anhydride 4['y-(di-n-propoxy-methylsilyl )-propyl anilide in 39 ml of anhydrous DMAis added dropwise. The reaction mixture is then stirred for a further 2hours at 2025C and is freed by filtration from the triethylaminehydrochloride which has precipitated. A solution of apolyamide-polyamide-acid prepolymer with a statistical distribution ofthe amide-acid units is obtained, which is used for the production offilms and coatings in accordance with the methods described; siliconcontent: 0.33 percent by weight.

The imidised prepolymer can be prepared as a powder from the abovesolution using 60 ml of acetic anhydride and 40 ml of pyridine,analogously to the procedure described in Example 17. The powder can beprocessed by the compression process at 280C to give sheets and bars ofgood flexural strength and good electrical properties.

EXAMPLE 33 Following the procedure described in Example 1, paragraph 1,30.5 g (0.15 mol) of isophthalic acid dichloride, 10.81 g (0.1 mol) ofm-phenylenediamine, 30.4 g (0.3 mol) of triethylamine and 21.94 g (0.1mol) of ('y-aminopropyl)di-n-propoxymethylsilane are reacted in 606 mlof anhydrous DMA. After filtering off the triethylamine hydrochlorideformed, the reaction solution is poured into a large excess of water,with vigorous stirring. A fine white precipitate separates out, which isfiltered off and dried for 16 hours at 50C/10 mm Hg. After grinding in amortar, a polyamide prepolymer is obtained in the form of a fine whitepowder.

This powder is'foamed by heating it in a closed mould to 200C for 10minutes. A white, hard foam of uniform pore size is obtained; siliconcontent: 6.64 percent by weight.

EXAMPLE 34 A 25 percent strength solution of the polyamide-acidprepolymer prepared according to Example 7 is completely evaporated todryness in vacuo at 50C. The resulting powder is pressed by thecompression-moulding process at C under a pressure of 500 kp/cm to givestandard bars. The compression mouldings are post-cured by heating themto 225C/10 mm Hg for 16 hours. Bars of good heat stability and excellentmechanical properties even at low temperatures are obtained.

What we claim is:

1. Crosslinked polyamides, polyimides or polyamideimides con'tainingsiloxane groups, with a silicon content of 0.1 to 17.0% by weight, whichare obtainable by 27 heating silicon-modified polyamide, polyamide-acidor polyamide-amide-acid prepolymers with an inherent viscosity of 0.04to 4.0, which have the formula I wherein X represents a structuralelement of the formula II O a (n) ll )m-l o C- c co0H a denotes a numberfrom 0 to 100, and the individual in, R R R;,, Q and Y independently ofone another denote the following: m denotes the number I or 2, R denotesa radical l t 1 r 1 H x H x with x denoting a number from 1 to 4, Rdenotes a carbocyclic-aromatic or heterocyclic-aromatic radical, whereinthe carbonamide and carboxyl groups are bonded to different ring carbonatoms and the carboxyl groups are each in the ortho-position to acarbonamide group, R denotes an aliphatic radical with at least 2 carbonatoms, or a cycloaliphatic, araliphatic, carbocyclic-aromatic orheterocyclic-aromatic radical, Q denotes methyl, phenyl or a -OYradical, with Y having the meaning indicated below, and Y denotes analkyl radical with l to 6 carbon atoms or a phenyl radical, orcorresponding cyclised derivatives, to temperatures between 50 and 350C.

2. Crosslinked polyamides, polyimides or polyamideimides containingsiloxane groups, according to claim 1, which are obtainable by heatingsilicon-modified prepolymers of the formula I, wherein the individual Rindependently of one another represent an unsubstituted monocyclic,fused polycyclic or non-fused bicyclic aromatic radical, the aromaticmucleii, in the latter case, being bonded to one another via thebridgemember O or CO, the individual R independently of one another representa monocyclic or non-fused bicyclic aromatic radical which is optionallysubstituted by halogen atoms or alkyl or alkoxy groups with 1-4 carbonatoms each, an unsubstituted monocyclic araliphatic radical or anunsubstituted aliphatic radical with 2-10 carbon atoms, or correspondingcyclised derivatives.

3. Crosslinked polyamides, polyimides or polyamideimides containingsiloxane groups, according to claim 1, which are obtainable by heatingsilicon-modified prepolymers of the formula I, wherein R represents thel,4- or l,3-phenylene radical, a benzene ring or the benzophenone ringsystem and R represents the 1,4- or 1,3-phenylene radical, the4,4-diphenylyl-ether radical or 4,4'-diphenylylmethane radical, withonly one of R and R denoting a l,4-phenylene radical, or correspondingcyclised derivatives.

4. Crosslinked polyamides, polyimides or polyamideimides containingsiloxane groups, according to claim 1, which are obtainable by heatingsilicon-modified prepolymers of the formula I, wherein, if a 2 l, theindividual R and R have the same meaning, m is the same for each radicalR or corresponding cyclised derivatives.

5. Crosslinked polyamide-imides containing siloxane groups, according toclaim 1, which are obtainable by heating silicon-modified prepolymers ofthe formula I, wherein X represents a structural element of the formulallb HOOC/ in which a denotes a number from 1 to 99 and the two R eachrepresent a benzene ring, with the carbonamide and carboxyl groups beingbonded to different ring carbon atoms and the carboxyl groups each beingin the ortho-position to the -CO-NI'I-R grouping, and the individual R RR Q and Y are identical, or corresponding derivatives with cyclisedterminal carboxylic acid groups.

6. Crosslinked polyamide-imides containing siloxane groups, according toclaim 1, which are obtainable by heating silicon-modified prepolymers ofthe formula I according to claim 1, wherein X represents a structuralelement of the formula Ilc in which a denotes a number from I to 99 andthe two R each denote a benzene ring, with the carbonamide groups andcarboxyl groups being bonded to different ring carbon atoms and thecarboxyl groups being each 29 in the ortho-position to the -CO-NII-Rgrouping, and the individual R R R Q and Y are identical, orcorresponding derivatives with cyclised terminal carboxylic acid groups.

7. Crosslinked polyamide-imides Containing siloxane groups, according toclaim 5, which are obtainable by heating siliconmodified prepolymers ofthe formula I, wherein R in each denotes a radical, the individual R andR are identical and one of R and R represents the 1,4-phenylene radicaland the other the l,3-phenylene radical or R and R each represent the1,3-phenylene radical, Q represents the methyl group and Y represents apropyl group or Q represents the ethoxy group and Y represents the ethylgroup, or corresponding derivatives with cyclised terminal carboxylicacid groups.

8. Crosslinked polyamides containing siloxane groups, according to claim1, which are obtainable by heating silicon-modified prepolymers of theformula I according to claim 1, wherein m in each case denotes thenumber 1, R in each case represents a radical, the individual R and Rare identical and one of R and R represents the 1,4-phenylene radicaland the other the 1,3-phenylene radical or R and R each represent the1,3-phenylene radical, Q represents the methyl group and Y represents apropyl group or Q represents the ethoxy group and Y represents the ethylgroup.

9. Crosslinked polyimides containing siloxane groups, according to claim1, which are obtainable by heating silicon-modified prepolymers of theformula I, wherein m in each case denotes the number 2, R in each caserepresents a 401 4. 1-CH24-5 or radical, R in each case denotes abenzene ring or the benzophenone ring system, R in each case denotes the4,4-diphenylyl-ether or the 4,4-diphenylylmethane radical, Q denotes themethyl group and Y denotes a propyl group or Q denotes the ethoxy groupand Y 30 denotes the ethyl group, or corresponding cyclised derivatives.

10. Crosslinked polyamide-imides containing siloxane groups, accordingto claim 1, which are obtainable by heating siliconmodified prepolymersof the formula I, wherein X represents a structural element of theformula IId COOI-I R (lid) in which R in each case represents a --LCH4CH 4 or radical, the individual R and R are respectively identical andone of R and R denotes the 1,4-phenylene radical and the other the1,3-phenylene radical, or R and R each denote the 1,3-phenylene radical,Q denotes the methyl group and Y denotes a propyl group or Q denotes theethoxy group and Y denotes the ethyl group, or corresponding derivativeswith cyclised terminal carboxylic acid groups.

12. Crosslinked polyamides, polyimides or polyamide-imides containingsiloxane groups, according to claim 1, which are obtainable by heatingto temperatures between and 225C.

1. CROSSLINKED POLYAMIDES, POLYMIDES OR POLYAMIDE-IMIDES CONTAININGSILOXANE GROUPS, WITH A SILICON CONTENT OF 0.1 TO 17.0% BY WEIGHT, WHICHARE OBTAINABLE BY HEATING SILICONMODIFIED POLYAMIDE, POLYMIDE-ACID ORPOLYAMIDE-AMIDE-ACID PREPOLYMERS WITH AN INHERENT VISCOSITY OF 0.04 TO4.0, WHICH HAVE THE FORMULA 1
 2. Crosslinked polyamides, polyimides orpolyamide-imides containing siloxane groups, according to claim 1, whichare obtainable by heating silicon-modified prepolymers of the formula I,wherein the individual R2 independently of one another represent anunsubstituted monocyclic, fused polycyclic or non-fused bicyclicaromatic radical, the aromatic mucleii, in the latter case, being bondedto one another via the bridge member -O- or -CO-, the individual R3independently of one another represent a monocyclic or non-fusedbicyclic aromatic radical which is optionally substituted by halogenatoms or alkyl or alkoxy groups with 1-4 carbon atoms each, anunsubstituted monocyclic araliphatic radical or an unsubstitutedaliphatic radical with 2-10 carbon atoms, or corresponding cyclisedderivatives.
 3. Crosslinked polyamides, polyimides or polyamide-imidescontaining siloxane groups, according to claim 1, which are obtainableby heating silicon-modified prepolymers of the formula I, wherein R2represents the 1,4- or 1,3-phenylene radical, a benzene ring or thebenzophenone ring system and R3 represents the 1,4- or 1,3-phenyleneradical, the 4,4''-diphenylyl-ether radical or 4,4''-diphenylylmethaneradical, with only one of R2 and R3 denoting a 1,4-phenylene radical, orcorresponding cyclised derivatives.
 4. Crosslinked polyamides,polyimides or polyamide-imides containing siloxane groups, according toclaim 1, which are obtainable by heating silicon-modified prepolymers ofthe formula I, wherein, if a > or = 1, the individual R2 and R3 have thesame meaning, m is the same for each radical R2, or correspondingcyclised derivatives.
 5. Crosslinked polyamide-imides containingsiloxane groups, according to claim 1, which are obtainable by heatingsilicon-modified prepolymers of the formula I, wherein X represents astructural element of the formula IIb
 6. Crosslinked polyamide-imidescontaining siloxane groups, according to claim 1, which are obtainableby heating silicon-modified prepolymers of the formula I according toclaim 1, wherein X represents a structural element of the formula IIc 7.Crosslinked polyamide-imides containing siloxane groups, according toclaim 5, which are obtainable by heating siliconmodified prepolymers ofthe formula I, wherein R1 in each denotes a
 8. Crosslinked polyamidescontaining siloxane groups, according to claim 1, which are obtainableby heating silicon-modified prepolymers of the formula I according toclaim 1, wherein m in each case denotes the number 1, R1 in each caserepresents a
 9. Crosslinked polyimides containing siloxane groups,according to claim 1, which are obtainable by heating silicon-modifiedprepolymers of the formula I, wherein m in each case denotes the number2, R1 in each case represents a
 10. Crosslinked polyamide-imidescontaining siloxane groups, according to claim 1, which are obtainableby heating siliconmodified prepolymers of the formula I, wherein Xrepresents a structural element of the formula IId
 11. Crosslinkedpolyamide-imides containing siloxane groups, according to claim 6, whichare obtainable by heating silicon-modified prepolymers of the formula I,wherein R1 in each case represents a
 12. Crosslinked polyamides,polyimides or polyamide-imides containing siloxane groups, according toclaim 1, which are obtainable by heating to temperatures between 150*and 225*C.